Organic Electronic Device and Method for the Production Thereof
An organic electronic device comprising: a substrate; (1), a first electrode; (2), a second electrode (4); and an electron-conducting region (3A, 3B) which is arranged between the first and; second electrodes and comprises an organic matrix material (3B) and a salt (3A) which comprises a metal cation and an at least trivalent anion.
This patent application claims the priority of German patent application DE 102009047880.9, the disclosure content of which is hereby incorporated by reference.
The present invention relates to organic electronic components, for example organic light-emitting devices, organic photosensitive devices, for example photovoltaic cells or photodetectors or organic transistors, for example organic field-effect transistors.
A widespread problem in organic electronic devices is, in the case of electroluminescent devices, for example, that of ensuring sufficient charge carrier injection through the anode and cathode to the at least one organic electroluminescent layer. In an OLED, the recombination of injected electrons and holes forms excitons which cause the organic electroluminescent layer to luminesce. The luminance, the efficiency and the lifetime of the OLEDs all depend greatly on the exciton density formed in the electroluminescent layer by charge carrier injection, and also on the quality of the charge carrier injection.
Analogously to organic light-emitting diodes (OLEDs), problems also occur in organic photosensitive devices, for example photovoltaic cells or photodetectors, with the charge carrier transport of the electrons and holes formed by means of exciton separation in the photoactive layer to the electrodes. Charge carrier transport also plays a major role in organic electronic devices with no optoelectronic application, for example in organic transistors such as organic field-effect transistors, and is one of the determining factors for the electrical properties.
The publication “Elucidation of the electron injection mechanism of evaporated caesium carbonate cathode interlayer for organic light emitting diodes” in the journal Applied Physics Letters (90, 2007) describes electron injection layers in OLEDs, which are formed by vacuum deposition of cesium carbonate and cause an increased efficiency of the OLED. The authors of this publication arrive at the conclusion that cesium carbonate decomposes in the course of vacuum deposition to metallic cesium which forms a thin layer which then serves as an electron injection layer. Other authors discuss a decomposition of the cesium carbonate to Cs2O and CO2. The outcome of this is that the anion of the salt used for vacuum deposition, i.e. carbonate, should not be involved in the electron injection.
One problem addressed by embodiments of the invention is that of specifying an organic electronic device in which electron transport is improved.
This object is achieved by an organic electronic device according to claim 1. Further claims are directed to preferred embodiments of the organic electronic device and to processes for production thereof.
One embodiment of the invention comprises an organic electronic device comprising
-
- a substrate,
- a first electrode,
- a second electrode, and
- an electron-conducting region which is arranged between the first and second electrodes and comprises
- an organic matrix material and a salt which comprises
- a metal cation and
- an at least trivalent anion.
In contrast to the publication already cited above in the introductory part of the description, the inventors have found that the nature of the anion of a metal salt is involved in charge carrier transport in an organic electronic device. The inventors assume that the anion of the metal salt which is used to produce the organic electronic device is incorporated into this device, and the valency, i.e. the charge of the anions, is of significance in the electron transport. Compared to the cesium carbonate used in the prior art, which has only a valency of 2, i.e. a double negative charge, it is possible in the case of an at least trivalent anion (triple negative charge) to observe an improvement in the electrical properties of the organic electronic device.
In one embodiment of an organic electronic device according to the invention, the electron-conducting region has at least two layers, of which a first layer comprises the matrix material and a second layer in contact with the first layer comprises the salt, this second layer, as what is called an electron injection layer, preferably being arranged closer to the electrode connected as the cathode than the first layer comprising the matrix material (see, for example,
In another preferred embodiment of the invention, the electron-conducting region may have an electron-conducting layer which comprises the organic matrix material into which the salt has been introduced as an n-dopant. In this embodiment, the improvements in the electrical properties are particularly distinctive.
It is possible to use the electron-conducting layer comprising the organic matrix material into which the salt has been introduced as an n-dopant, for example, as a charge carrier transport layer which transports electrones from one region to another region of an organic electronic device. In addition, the electron-conducting layer may also be part of what is called a charge generation layer (CGL), in which, for example, a doped hole transport layer and a doped electron transport layer are present and may be separated by a thin intermediate layer of metal, for example, or else are in direct contact with one another. Such a CGL may, for example, connect different OLED subcells with one another in an OLED tandem cell.
The inventors have found that salts with at least trivalent anions, i.e., for example, tri- or tetravalent anions, as dopants in layers comprising matrix materials have advantages over dopants composed of salts with only divalent anions, for example cesium carbonate. For example, it is possible to use salts with at least trivalent anions as a dopant in electron-transporting matrix materials in concentrations up to five times lower than salts with divalent anions. In addition, current-voltage characteristics show that the improvement in conductivity on doping with salts with at least trivalent anions is at least one order of magnitude better than in the case of salts having only divalent anions (see, for example, a comparison of
In the case that the salt has been introduced as an n-dopant into the layer comprising the matrix material, it is advantageous when the n-dopant is present in a concentration of 1 to 50% by volume, preferably 5 to 15% by volume, in the organic matrix material. Percentage by volume concentrations within this range lead to a particularly marked improvement in the electrical properties, for example in the current-voltage characteristics. This is particularly marked in the case of use of BCP as the matrix material.
The metal cation of the salt may be selected from:
-
- monovalent metal cations,
- alkaline earth metal cations,
- zirconium cations or combinations thereof.
The inventors have found that particularly monovalent metal cations, for example alkali metal cations such as Rb(I) and Cs(I), or Ag(I), Cu(I), Tl(I) and alkaline earth metal cations are good dopants in combination with at least trivalent anions. These salts of trivalent anions can also be vaporized without decomposition.
The at least trivalent anion may be selected, for example, from
-
- phosphate anions PO43−,
- vanadate anions VO43−,
- silicate anions 51044−,
- at least trivalent anionic polyvalent organic anions, for example the trianion of 1,3,5-benzenetricarboxylic acid or the tetraanion of naphthalenetetracarboxylic acid or at least trivalent organic acids, for example the tetraanion of methanetetracarboxylic acid or the trianion of methanetricarboxylic acid.
The corresponding cesium salts of methanetetracarboxylic acid and of methanetricarboxylic acid have the following structures:
The organic anions may, for example, also have aromatic rings with nitrogen atoms. All abovementioned anions and cations can also be used in combination.
The inventors have found that the abovementioned cations and anions, particularly phosphate, have positive effects on the electrical properties of an organic electronic device when they are used as a dopant in electron-transporting layers.
In the case that the salt is used as an n-dopant in a layer comprising the organic matrix material, the undissociated salt can, for example, be coordinated to the organic matrix material via the metal cation (see, for example,
It is additionally conceivable that the dopant, for example in a covaporization of the matrix material and the salt, forms a coordination compound between the metal cation of the salt and the organic matrix material as a ligand upon dissociation of the salt, in which case the anion is then intercalated into this matrix (see, for example,
In a further embodiment of an organic electronic device according to the invention, the organic matrix material comprises a heterocyclic nitrogen containing compound. This compound may comprise, for example, pyridine base structures, for example 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP). Heterocyclic nitrogen containing compounds are particularly suitable for serving as ligands for the metal cations of the n-dopant salt and are generally also good electron conductors.
In a further embodiment of the invention, the organic matrix material comprises a repeating unit with the following general formula:
where
-
- the ring members A to F are each independently C or N, with the proviso that a maximum of two nitrogen atoms may be present,
- n is an integer from 2 to 8, where the free valences of the ends of the chains of the repeat units may each independently be saturated by H, methyl, phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl,
R1 to R4 may each independently be H, methyl, phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl, and/or R1 and R2 or R3 and R4 may together form butadiene or azabutadiene units, such that a fused 6-membered ring system is formed and the repeating units may be bonded by ethylene or azomethine units between the nth and (n+1)th ring to form phenanthrene or azaphenanthrene units.
Such oligopyridyl- and/or oligopyridinylarenes are particularly suitable since they coordinate well to the dopants and are disclosed, for example, in PCT application WO2008/058929, to which reference is made in respect of these materials. The charge carrier transport properties of the matrix materials mentioned can be controlled via the number of nitrogen atoms in the ring system.
The organic matrix material may be selected from the following specific compounds and combinations thereof:
Further options are also the following matrix materials, and combinations thereof:
- 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole),
- 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole,
- 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP),
- 8-hydroxyquinolinatolithium,
- 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole,
- 1,3-bis[2-(2,2′-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]benzene,
- 4,7-diphenyl-1,10-phenanthroline,
- 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole,
- bis(2-methyl-8-quinolinato)-4-(phenylphenolato)aluminum,
- 6,6′-bis[5-biphenyl-4-yl)-1,3,4-oxadiazo-2-yl]-2,2′-bipyridyl,
- 2-phenyl-9,10-di(naphthalen-2-yl)anthracene,
- 2,7-bis[2-(2,2′-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]
- 9,9-dimethylfluorene,
- 1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl)benzene,
- 2-(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline,
- 2,9-bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline,
- tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane,
- 1-methyl-2-(4-(naphthalen-2-yl)phenyl)-1H-imidazo[4,5-f][1,10]-phenanthroline,
- siloles with silacyclopentadiene units.
Preferred salts for dopants are particularly alkali metal salts of the phosphates, for example cesium phosphate.
A further embodiment of the invention provides an organic electronic device which is configured as an organic electroluminescent diode (OLED) and further comprises an organic electroluminescent layer between the electron-conducting region and one of the electrodes. The electroluminescent (EL) layer is arranged in the layer stack of the OLED such that the electron-conducting region is between the EL layer and the electrode connected as the cathode. In such a configuration of an OLED, particularly good electron transport from the cathode to the organic EL layer is ensured.
In addition, the organic electronic device of the present invention may also be configured as an organic photosensitive device, in which case an organic photoactive layer, for example a bulk heterojunction, is present between an n-conducting and a p-conducting material. The n-conducting material may, for example, be fullerene C60 which, for example, has been mixed with p-conducting polymers such as polyparaphenylenevinylene or has been shaped in separate layers applied one on top of another. In the case of such an organic photosensitive device, the inventive electron-conducting region is then likewise arranged between the organic photoactive layer and the electrode connected as the cathode, and thus enables particularly efficient transport of the electrons formed by incident light from excitons away from the organic photoactive layer.
A further example of an organic electronic device is an organic transistor, for example a field-effect transistor, in which an organic semiconductor which may, for example, comprise an electron-conducting layer in accordance with the invention with the salt as a dopant may be present (see, for example,
The invention further provides a process for producing an organic electronic device, comprising the process steps of:
A) providing a substrate with a first electrode,
B) applying an electron-conducting region to the first electrode,
C) applying a second electrode in electrically conductive contact with the electron-conducting layer,
-
- wherein the electron-conducting layer is applied by vaporizing an organic matrix material and a salt which comprises
- metal cations and
- an at least trivalent anion.
More preferably, in process step B), the electron-conducting region is obtained by means of vapor deposition, more preferably by means of physical vapor deposition (PVD). In the case that the electron-conducting layer is a layer of an organic matrix material with the salt as an n-dopant, covaporization of the salt and of the organic matrix material is preferred. The salts with the at least trivalent anion are easy to vaporize, and frequently just a few residues, if any, are observed. Due to the high, at least triple negative charge present in the anion, such salts should be difficult to vaporize. The inventors, however, have found that it is surprisingly possible, for example, to vaporize the cesium phosphate salt by electrically heated molybdenum boats practically residue-free. The vaporization properties of cesium phosphate are similar to those of the lithium fluoride salt, but this only has a single negatively charged fluoride anion. Cesium carbonate, which is known from the prior art, in contrast, forms non-vaporizable residues under the same conditions.
The invention also provides an electron-conducting composition comprising:
-
- an electron-conducting matrix material, which may comprise, for example, the compounds already mentioned above, and
- a salt as an n-dopant, said salt comprising
- an at least trivalent anion and
- a cation.
Hereinafter, aspects of the present invention will be explained in detail with reference to working examples and figures.
The schematic cross section shown in
A comparison of the current-voltage characteristics of
It is clearly evident that the doping with cesium methanetetracarboxylate also results in observation of distinct improvements in the electrical behavior of the electron-conducting layers.
Synthesis of the Cesium Salts of Methanetetracarboxylic Acid and of Methanetricarboxylic Acid:Under inert conditions, 1 mol of diethyl malonate is added dropwise to 1 mol of freshly prepared sodium ethoxide solution. Thereafter, 1 mol of ethyl chloroformate is added dropwise and the mixture is heated at 50° C. for 1 h. The reaction mixture is then admixed again with 1 mol of freshly prepared sodium ethoxide solution, followed by 1 mol of ethyl chloroformate. Finally, the mixture is heated once again at 50° C. for 1 h and at reflux for 1 h. The reaction mixture is acidified slightly with glacial acetic acid and concentrated down to an oil on a rotary evaporator. The residue is then admixed with water and the tetracarboxylic ester is extracted by means of ether. The dried ether phase is freed completely of the ether on a rotary evaporator and the remaining oil is fractionated under reduced pressure, b.p.: 170° C./12 mbar. The tetraethyl methanetetracarboxylate fraction is stirred with the equivalent amount of cesium hydroxide in water until the two phases of the biphasic mixture have dissolved in one another. The water solvent is completely distilled off on a rotary evaporator and the residue is recrystallized from methanol. The white product which crystallizes is filtered off with suction and, after drying under reduced pressure, is dried in a drain sublimator in an argon stream, vacuum (10-2 mbar) at 300° C. The dried cesium salt of methanetetracarboxylic acid is harvested in a glovebox without prior air exposure (grayish-white powder with a sublimation temperature of >625° C.).
It is also possible analogously to prepare the cesium salt of methanetricarboxylic acid, except that the synthesis is stopped at the first alkylation stage.
The invention is not restricted by the description with reference to working examples. Instead, the invention encompasses every novel feature and every combination of features, which especially includes any combination of features in the claims, even if the feature or this combination itself is not mentioned explicitly in the claims or working examples.
Claims
1. An organic electronic device comprising:
- a substrate;
- a first electrode;
- a second electrode; and
- an electron-conducting region which is arranged between the first and second electrodes and comprises
- an organic matrix material and a salt which comprises
- a metal cation and
- an at least trivalent anion.
2. The electronic device according to claim 1, wherein the electron-conducting region comprises an electron-conducting layer which comprises the organic matrix material and in which the salt has been introduced as an n-dopant.
3. The electronic device according to claim 2,
- wherein the n-dopant is present in the organic matrix material in a concentration of 1 to 50% by volume, preferably 5 to 15% by volume.
4. The electronic device according to claim 2,
- wherein the salt is coordinated to the organic matrix material via the metal cation.
5. The electronic device according to claim 2,
- wherein a coordination compound between the metal cation and the organic matrix material is present in the electron-conducting layer, into which compound the anion has been intercalated.
6. The electronic device according to claim 2,
- wherein the electron-conducting layer is obtainable by covaporization of a salt of the anion and of the metal cation with the organic matrix material.
7. The electronic device according to claim 1,
- wherein the metal cation is selected from: alkali metal cations, alkaline earth metal cations, Ag+, Cu+ and Tl+, and combinations thereof.
8. The electronic device according to claim 1,
- wherein the organic matrix material comprises a heterocyclic nitrogen containing compound.
9. The electronic device according to claim 1, where
- wherein the organic matrix material has a repeating unit with the following general formula:
- the ring members A to F are each independently C or N, with the proviso that a maximum of two nitrogen atoms may be present,
- n is an integer from 2 to 8, where the free valences of the ends of the chains of the repeat units may each independently be saturated by H, methyl, phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl,
- R1 to R4 may each independently be H, methyl, phenyl, 2-pyridyl, 3-pyridyl or 4-pyridyl, and/or R1 and R2 or R3 and R4 may together form butadiene or azabutadiene units, such that a fused 6-membered ring system is formed and the repeating units may be bonded by ethylene or azomethine units between the nth and (n+1)th ring to form phenanthrene or azaphenanthrene units.
10. The electronic device according to claim 1
- wherein the organic matrix material is selected from:
- or combinations thereof.
11. The electronic device according claim 1, wherein the organic matrix material is selected from the following compounds:
- 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole),
- 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole,
- 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP),
- 8-hydroxyquinolinatolithium,
- 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole,
- 1,3-bis[2-(2,2′-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]benzene,
- 4,7-diphenyl-1,10-phenanthroline,
- 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole,
- bis(2-methyl-8-quinolinato)-4-(phenylphenolato)aluminum,
- 6,6′-bis[5-biphenyl-4-yl)-1,3,4-oxadiazo-2-yl]-2,2′-bipyridyl,
- 2-phenyl-9,10-di(naphthalen-2-yl)anthracene,
- 2,7-bis[2-(2,2′-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]-9,9-dimethylfluorene,
- 1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl)benzene,
- 2-(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline,
- 2,9-bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline,
- tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane,
- 1-methyl-2-(4-(naphthalen-2-yl)phenyl)-1H-imidazo[4,5-f][1,10]-phenanthroline,
- siloles with silacyclopentadiene units.
12. The electronic device according to claim 1, in the form of an organic electroluminescent device, further comprising
- an organic electroluminescent layer between the electron-conducting region and one of the electrodes.
13. The electronic device according to claim 1, in the form of an organic photosensitive device, further comprising
- an organic photoactive layer between the electron-conducting region and one of the electrodes.
14. A process for producing an organic electronic device, comprising the process steps of:
- A) providing a substrate with a first electrode;
- B) applying an electron-conducting region to the first electrode;
- C) applying a second electrode in electrically conductive contact with the electron-conducting region;
- wherein the electron-conducting region is applied by vaporizing an organic matrix material and a salt which comprises
- metal cations and
- an at least trivalent anion.
15. An electron-conducting composition comprising:
- an electron-conducting matrix material, and
- a salt as an n-dopant, said salt comprising
- an at least trivalent anion and
- a cation.
16. An organic electronic device comprising:
- a substrate;
- a first electrode;
- a second electrode; and
- an electron-conducting region which is arranged between the first and second electrodes and comprise an organic matrix material and a salt which comprises a metal cation, and
- an at least trivalent anion, which is selected from a group consisting of phosphate anions PO43−, and at least trivalent anionic polyvalent organic anions.
17. A process for producing an organic electronic device, comprising the process steps of:
- A) providing a substrate with a first electrode;
- B) applying an electron-conducting region to the first electrode; and
- C) applying a second electrode in electrically conductive contact with the electron-conducting region,
- wherein the electron-conducting region is applied by vaporizing an organic matrix material and a salt which comprises
- metal cations and
- an at least trivalent anion, which is selected from a group consisting of: phosphate anions PO43−, and at least trivalent anionic polyvalent organic anions.
Type: Application
Filed: Sep 30, 2010
Publication Date: Nov 15, 2012
Patent Grant number: 9520570
Inventors: Guenter Schmid (Hemhofen), Jan Hauke Wemken (Nuernberg), Andreas Kanitz (Hoechstadt)
Application Number: 13/499,542
International Classification: H01L 51/30 (20060101); H01B 1/00 (20060101); H01L 51/40 (20060101);